WO2017171063A1 - Feuille de mousse de résine de polyoléfine réticulée et son procédé de production - Google Patents

Feuille de mousse de résine de polyoléfine réticulée et son procédé de production Download PDF

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WO2017171063A1
WO2017171063A1 PCT/JP2017/013767 JP2017013767W WO2017171063A1 WO 2017171063 A1 WO2017171063 A1 WO 2017171063A1 JP 2017013767 W JP2017013767 W JP 2017013767W WO 2017171063 A1 WO2017171063 A1 WO 2017171063A1
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Prior art keywords
polyolefin resin
sheet
crosslinked polyolefin
foam sheet
resin foam
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PCT/JP2017/013767
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English (en)
Japanese (ja)
Inventor
麻美 松本
健人 永井
和幸 矢原
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積水化学工業株式会社
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Priority to KR1020187025931A priority Critical patent/KR102062297B1/ko
Priority to JP2017520993A priority patent/JP6496407B2/ja
Priority to CN201780004910.9A priority patent/CN108431106B/zh
Publication of WO2017171063A1 publication Critical patent/WO2017171063A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the present invention relates to a crosslinked polyolefin resin foam sheet and a method for producing the same.
  • the screen of a small electronic device (mobile phone, camera, game, electronic notebook, etc.) has a structure in which a display unit protection panel is installed on the display unit (LTD, etc.) of the housing. Adhesive tape is used to attach the frame part to the outside of the screen.
  • Patent Document 1 discloses that a foamed polyolefin resin sheet containing a thermally decomposable foaming agent is foamed and crosslinked, and has a thickness of 0.05 to An adhesive tape using a 2 mm cross-linked polyolefin resin foam sheet is disclosed.
  • the frame portion on the outside of the screen tends to be narrowed, and the tape width of the adhesive tape used for the frame portion also tends to be narrowed.
  • conventional adhesive tapes using crosslinked polyolefin resin foam sheets cannot provide sufficient strength to withstand impacts such as dropping when the tape width is narrowed to 0.7 mm or less.
  • the sheet, which is a base material constituting the tape, has a drawback that the material is easily broken.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is, for example, sufficient strength to withstand an impact such as dropping even when the tape width is narrowed to 0.7 mm or less. It is providing the crosslinked polyolefin-type resin foam sheet which can implement
  • the present inventors have found that the object can be achieved by using a crosslinked polyolefin resin foamed sheet in which the strain hardening degree and the shear viscosity are in specific ranges, respectively. .
  • the present invention has been completed based on such findings.
  • the present invention provides the following [1] to [7].
  • [1] A crosslinked polyolefin resin foamed sheet in which closed cells are formed, and the strain hardening degree obtained from the uniaxial elongation viscosity at a strain rate of 0.2 to 1.0 [1 / s] at the temperature at the time of foaming. ( ⁇ max) is 0.1 or more and less than 0.5, and the slope m of the linear region of the shear viscosity ⁇ + and the time t [s] is 0.7 ⁇ m ⁇ 1.0 at the foaming temperature.
  • a crosslinked polyolefin resin foamed sheet that satisfies the above relationship and has an average cell diameter in the MD direction and TD direction of 120 ⁇ m or less.
  • a method for producing a crosslinked polyolefin resin foam sheet comprising a step.
  • a crosslinked polyolefin resin foam sheet capable of realizing an adhesive tape having sufficient strength to withstand impacts such as dropping even when the tape width is narrowed to 0.7 mm or less. be able to.
  • the cross-linked polyolefin resin foam sheet according to the present invention is a cross-linked polyolefin resin foam sheet obtained by subjecting a polyolefin resin processed into a sheet shape to a cross-linking treatment and a foaming treatment.
  • the strain hardening degree ( ⁇ max) determined from the uniaxial elongation viscosity at 2 to 1.0 [1 / s] is 0.1 or more and less than 0.5, and the shear viscosity ⁇ + and time at the temperature at the time of foam formation.
  • the slope m of the linear region of t [s] satisfies the relationship 0.7 ⁇ m ⁇ 1.0.
  • the closed cell of the crosslinked polyolefin resin foam sheet has an average cell diameter of MD and TD of 120 ⁇ m or less, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and an average cell diameter of ZD of 80 ⁇ m or less, preferably 50 m or less, more preferably 40 ⁇ m.
  • This is a so-called “microcell”.
  • the lower limit value of the average bubble diameter is not particularly limited, but the average bubble diameter of MD and TD is, for example, 5 ⁇ m or more, preferably 20 ⁇ m or more.
  • the average bubble diameter of ZD is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more.
  • bubbles are closed cells means that the ratio of closed cells to all bubbles (referred to as closed cell ratio) is 70% or more, preferably 75% or more, more preferably 90% or more.
  • the closed cell ratio can be determined based on JIS K7138 (2006) and ASTM D2856 (1998).
  • Commercially available measuring instruments include a dry automatic densitometer Accupic 1330 and the like.
  • the closed cell ratio is measured, for example, in the following manner.
  • a test piece having a flat square shape with a side of 5 cm and a constant thickness is cut out from the crosslinked polyolefin resin foam sheet.
  • the thickness of the test piece is measured, the apparent volume V 1 of the test piece is calculated, and the weight W 1 of the test piece is measured.
  • the apparent volume V 2 occupied by the bubbles is calculated based on the following formula.
  • the density of the resin constituting the test piece is 1 g / cm 3 .
  • Apparent volume occupied by bubbles V 2 V 1 ⁇ W 1
  • the test piece is submerged in distilled water at 23 ° C.
  • the crosslinking degree of the crosslinked polyolefin resin foamed sheet is preferably 5 to 80% by mass, and more preferably 15 to 75% by mass. Further, the degree of crosslinking is more preferably 35 to 70% by mass.
  • the degree of crosslinking is preferably 5 to 80% by mass, and more preferably 15 to 75% by mass. Further, the degree of crosslinking is more preferably 35 to 70% by mass.
  • the degree of crosslinking is preferably 5 to 80% by mass, and more preferably 15 to 75% by mass. Further, the degree of crosslinking is more preferably 35 to 70% by mass.
  • the degree of crosslinking is less than 5% by mass, the degree of strain hardening is large, the elongational viscosity is reduced, the bubble growth at the time of foaming is promoted, and the impact resistance is lowered when used in a narrow width. From such a viewpoint, the degree of crosslinking is preferably within the above range.
  • a crosslinking degree is measured by the measuring method mentioned later
  • the strain hardening degree ( ⁇ max) obtained from the uniaxial elongation viscosity at a strain rate of 0.2 to 1.0 [1 / s] at the foaming temperature is 0.1 or more and less than 0.5, and the time 0
  • the slope m of the linear region of the shear viscosity ⁇ + and the extension time t [s] at 1 to 100 [s] satisfies the relationship 0.7 ⁇ m ⁇ 1.0.
  • the elongational viscosity can be divided into a region that gradually increases without depending on the strain rate and a region that rapidly increases depending on the strain rate.
  • the slowly increasing region is called the linear region, and the extensional viscosity is equal to 3 times the shear viscosity.
  • the phenomenon of rapidly increasing is called strain hardening, and the degree is expressed by the degree of strain hardening.
  • the material breakage of the crosslinked polyolefin resin foamed sheet is a phenomenon that occurs when stress is concentrated on a specific portion when an impact is applied, and that is the starting point. As described in the background art column, when the tape width is narrowed to 0.7 mm or less, the force applied per unit area of the tape increases in the event of a drop impact, etc.
  • the strain hardening degree is measured by the measurement method described later in the Example column, and the shear viscosity is determined by the method described later in the Example column.
  • the thickness of the crosslinked polyolefin resin foamed sheet is preferably 50 to 300 ⁇ m, more preferably 70 to 150 ⁇ m.
  • the thickness is 50 ⁇ m or more, it is easy to ensure the mechanical strength and flexibility of the crosslinked polyolefin resin foam sheet.
  • the thickness is 300 ⁇ m or less, it is possible to reduce the film thickness, and it can be suitably used for a miniaturized electronic device.
  • the expansion ratio of the crosslinked polyolefin resin foamed sheet is 1.3 to 2.3 cm 3 / g.
  • the expansion ratio is less than 1.3 cm 3 / g, the flexibility is lowered and the impact absorbability is deteriorated, and the crosslinked polyolefin resin foam sheet can sufficiently exhibit the function as a sealing material and an impact material. There is a risk of disappearing.
  • it exceeds 2.3 cm 3 / g the mechanical strength of the crosslinked polyolefin resin foamed sheet may not be improved.
  • the expansion ratio is more preferably 1.5 to 2.0 cm 3 / g.
  • the density of the foamed sheet is obtained according to JIS K7222, and the reciprocal thereof is taken as the foaming ratio.
  • the 25% compressive strength of the crosslinked polyolefin resin foamed sheet is preferably 400 to 2000 kPa, and more preferably 600 to 1800 kPa. By setting the 25% compressive strength to 2000 kPa or less, the cross-linked polyolefin resin foam sheet has shock absorbing performance and can be used as a cushioning material or a sealing material. In addition, 25% compressive strength means what measured the crosslinked polyolefin resin foam sheet based on JISK6767.
  • polyolefin resin examples of the polyolefin resin used for forming the above-mentioned crosslinked polyolefin resin foam sheet include polyethylene resins polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene compound, and a chromium oxide compound, preferably a polymerization of a metallocene compound.
  • a polyethylene resin polymerized with a catalyst is used.
  • the polyethylene-based resin used for forming the crosslinked polyolefin resin foamed sheet of the present invention is a straight-chain obtained by copolymerizing ethylene and a small amount of ⁇ -olefin as required using a polymerization catalyst such as a metallocene compound.
  • a chain low density polyethylene is preferred.
  • linear low-density polyethylene high flexibility is obtained in the obtained crosslinked polyolefin resin foamed sheet, and the crosslinked polyolefin resin foamed sheet can be made thinner.
  • the ⁇ -olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. Of these, ⁇ -olefins having 4 to 10 carbon atoms are preferred.
  • the density of the polyethylene resin from the viewpoint of flexibility to the crosslinked polyolefin resin foam sheet produced is obtained, preferably 0.870 ⁇ 0.910g / cm 3, 0.875 ⁇ 0.907g / cm 3 Gayori 0.880 to 0.905 g / cm 3 is more preferable.
  • the polyethylene resin a plurality of polyethylene resins can be used, and a polyethylene resin outside the above density range may be added. By using the linear low density polyethylene as described above, the strain hardening degree and m can be easily within the above ranges.
  • Suitable metallocene compounds in the present invention include compounds such as bis (cyclopentadienyl) metal complexes having a structure in which a transition metal is sandwiched between ⁇ -electron unsaturated compounds. More specifically, tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum have one or more cyclopentadienyl rings or their analogs as ligands (ligands). Can be mentioned. Such metallocene compounds have uniform active site properties and each active site has the same activity.
  • a polymer synthesized using a metallocene compound has high uniformity in molecular weight, molecular weight distribution, composition, composition distribution, etc., so when a sheet containing a polymer synthesized using a metallocene compound is crosslinked, the crosslinking is uniform. Proceed to. Since the uniformly crosslinked sheet can be stretched uniformly, the thickness of the crosslinked polyolefin resin foamed sheet can be made uniform.
  • Examples of the ligand include a cyclopentadienyl ring and an indenyl ring. These cyclic compounds may be substituted with a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group.
  • Examples of the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Various cetyl groups, phenyl groups and the like.
  • the “various” means various isomers including n-, sec-, tert-, and iso-. Moreover, what polymerized the cyclic compound as an oligomer may be used as a ligand. In addition to ⁇ -electron unsaturated compounds, monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
  • monovalent anion ligands such as chlorine and bromine or divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
  • metallocene compounds containing tetravalent transition metals and ligands include, for example, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, dimethyl And silyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride.
  • the metallocene compound exhibits an action as a catalyst in the polymerization of various olefins by combining with a specific cocatalyst (co-catalyst).
  • specific cocatalyst include methylaluminoxane (MAO) and boron compounds.
  • the proportion of the cocatalyst used with respect to the metallocene compound is preferably 100,000 to 1,000,000 mole times, more preferably 50 to 5,000 mole times.
  • the Ziegler-Natta compound is a triethylaluminum-titanium tetrachloride solid composite, which is obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating with various electron donors and electron acceptors.
  • a method of combining a composition, an organoaluminum compound, and an aromatic carboxylic acid ester see JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907), halogens Method of supported catalyst in which magnesium tetrachloride is brought into contact with magnesium tetrachloride and various electron donors (see JP-A-57-63310, JP-A-63-43915, JP-A-63-83116), etc. What was manufactured by is preferable.
  • the above linear low density polyethylene may be used alone, but other polyolefin resins are included. Also good.
  • other polyolefin resins include other polyethylene resins such as ethylene-vinyl acetate copolymer containing 50% by mass or more of ethylene, polypropylene resins, and the like. These may be used alone or in combination of two or more.
  • polypropylene resin examples include polypropylene and a propylene- ⁇ -olefin copolymer containing 50% by mass or more of propylene. These may be used alone or in combination of two or more.
  • Specific examples of the ⁇ -olefin constituting the propylene- ⁇ -olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1- Among these, ⁇ -olefins having 6 to 12 carbon atoms are preferable.
  • the ratio of the other polyolefin resin to the linear low-density polyethylene is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • the method for producing the crosslinked polyolefin resin foamed sheet is not particularly limited, and can be produced, for example, by a production method including the following steps (1) to (4).
  • ⁇ Process (1) Process (2) for producing a polyolefin resin sheet by supplying an additive containing a polyolefin resin and a pyrolytic foaming agent to an extruder, melt-kneading, and extruding it into a sheet form from the extruder Steps (3) of irradiating the polyolefin resin sheet with ionizing radiation to crosslink the foamable polyolefin resin sheet to a degree of crosslinking of 5% by mass or more Process / process (4) of heating a crosslinked polyolefin resin sheet and foaming a pyrolytic foaming agent to form a microcell After forming the microcell, a process of stretching the microcell and obtaining a crosslinked polyolefin resin foamed sheet
  • the pyrolytic foaming agent is not particularly limited, and examples thereof include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide and the like. Of these, azodicarbonamide is preferred.
  • a thermal decomposition type foaming agent may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the thermally decomposable foaming agent added to the foamable polyolefin resin composition is preferably 1 to 8 parts by mass, more preferably 2 to 6 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the amount of the pyrolytic foaming agent is within this range, the foamability of the expandable polyolefin resin sheet is improved, and a crosslinked polyolefin resin foam sheet having a desired expansion ratio can be obtained.
  • by setting it as 2 mass parts or more a bubble becomes large and it becomes possible to set the thickness of an average cell wall to the target range, enlarging an average bubble diameter.
  • the foaming method is not limited to the above, and physical foaming with butane gas or the like may be used.
  • an antioxidant such as 2,6-di-t-butyl-p-cresol
  • a foaming aid such as zinc oxide
  • a cell nucleus modifier such as 1,3-di-t-butyl-p-cresol
  • a heat stabilizer such as 1,3-di-t-butyl-p-cresol
  • Colorants, flame retardants, antistatic agents, fillers, and the like may be added within a range that does not impair the physical properties of the crosslinked polyolefin resin foam sheet.
  • the size of the bubble diameter can be adjusted by the bubble nucleus adjusting material.
  • a method of crosslinking the expandable polyolefin resin composition a method of irradiating the expandable polyolefin resin sheet with ionizing radiation such as electron beam, ⁇ ray, ⁇ ray, ⁇ ray and the like is used.
  • the irradiation dose of the ionizing radiation may be adjusted within a range of, for example, 2 to 75 Mrad so that the degree of crosslinking can be adjusted to 5 to 80% by mass, preferably 15 to 75 Mrad, and preferably 30 to 70 Mrad. Is more preferable. In some cases, it may be 2 to 15 Mrad or 3 to 12 Mrad.
  • the stretching of the foamed sheet may be performed after foaming the foamable polyolefin resin sheet to obtain the foamed sheet, or may be performed while foaming the foamable polyolefin resin sheet.
  • the foamed sheet is continuously stretched while maintaining the molten state during foaming without cooling the foamed sheet.
  • the foamed sheet may be heated again to be in a molten or softened state and then stretched.
  • the draw ratio in the MD direction of the crosslinked polyolefin resin foamed sheet is preferably 1.1 to 2.0 times, and more preferably 1.2 to 1.8 times.
  • the draw ratio in the MD direction of the crosslinked polyolefin resin foamed sheet is set to the above lower limit value or more, the flexibility and tensile strength of the crosslinked polyolefin resin foamed sheet are likely to be good.
  • the foamed sheet is prevented from breaking during stretching, or the foaming gas escapes from the foamed sheet being foamed and the foaming ratio is significantly reduced. And tensile strength is improved, and the quality is easily uniform.
  • an adhesive layer can be provided on at least one surface of the crosslinked polyolefin resin foamed sheet to obtain an adhesive tape.
  • the thickness of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape is preferably 5 to 200 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is more preferably 7 to 150 ⁇ m, still more preferably 10 to 100 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape is in the range of 5 to 200 ⁇ m, the thickness of the structure fixed using the pressure-sensitive adhesive tape can be reduced.
  • stacked and integrated on the one or both surfaces of a crosslinked polyolefin resin foam sheet For example, an acrylic adhesive, a urethane adhesive, a rubber adhesive, etc. are used. be able to.
  • a pressure-sensitive adhesive is applied to at least one surface of the cross-linked polyolefin resin foam sheet using a coater or the like.
  • Examples thereof include a method of applying, a method of spraying and applying a pressure-sensitive adhesive using at least one surface of a cross-linked polyolefin resin foam sheet, a method of applying a pressure-sensitive adhesive using a brush on at least one surface of the cross-linked polyolefin resin foam sheet, and the like.
  • the measuring method of each physical property in this specification is as follows.
  • the average bubble diameter is measured in the following manner. What measured the foam sheet for a measurement in 50 mm square was prepared as the foam sample for a measurement. This was immersed in liquid nitrogen for 1 minute, and then cut with a razor blade in the thickness direction along the MD, TD, and ZD directions. This cross-section is taken with a digital microscope (Keyence Co., Ltd. “VHX-900”), and a 200 times magnified photograph is taken. All of the cross sections present in a length of 2 mm in each of the MD, TD, and ZD directions. The cell diameter of each closed cell was measured, and the operation was repeated 5 times. And the average value of all the bubbles was made into the average bubble diameter of MD direction, TD direction, and ZD direction. Moreover, the largest bubble length was made into the largest bubble diameter among the measured bubble diameters.
  • a sheet having a thickness of 290 ⁇ m was cut into a width of 1 cm and a length of 3 cm.
  • Uniaxial elongational viscosity was measured at a constant strain of a temperature of 250 ° C. and strain rates of 0.3, 0.5, and 1.0 (1 / s).
  • a viscoelasticity measuring apparatus ARES manufactured by Rheometric Scientific F.E.
  • the sample was measured by cutting a sheet having a thickness of 290 ⁇ m into a circle having a diameter of 8 mm and setting it on a parallel disk plate having a diameter of 8 mm.
  • ⁇ + is the shear viscosity
  • strain hardening degree ⁇ max is expressed by the following formula.
  • ⁇ E is the extensional viscosity in the non-linear region
  • 3 ⁇ + is the shear viscosity ⁇ + (t) determined by the method described in the following document (1), for example, from the storage elastic modulus and loss elastic modulus obtained by shear viscosity measurement
  • the linear elongational viscosity calculated from ⁇ , ⁇ is the strain amount.
  • the weight average molecular weight was measured by a GPC method using “2690 Separations Model” manufactured by Water Co. as a column, which was 600,000. 15 parts by mass of polymerized rosin ester having a softening point of 135 ° C., ethyl acetate (Fuji Kagaku) with respect to 100 parts by mass of the solid content of the acrylic copolymer (z) contained in the solution of the obtained acrylic copolymer (z) 125 parts by mass of Yakuhin Co., Ltd.
  • an isocyanate-based cross-linking agent manufactured by Tosoh Corporation, Coronate L45
  • An isocyanate-based cross-linking agent manufactured by Tosoh Corporation, Coronate L45
  • the degree of crosslinking of the acrylic pressure-sensitive adhesive was 33% by mass.
  • a release paper having a thickness of 150 ⁇ m was prepared, an adhesive (Z) was applied to the release-treated surface of the release paper, and dried at 100 ° C. for 5 minutes to form an acrylic adhesive layer having a thickness of 50 ⁇ m. This acrylic pressure-sensitive adhesive layer was bonded to the surface of a cross-linked polyolefin resin foam sheet substrate.
  • FIG. 1 shows a schematic diagram of an impact resistance test apparatus.
  • the impact resistance test apparatus was produced by the following procedure. First, the double-sided pressure-sensitive adhesive tape obtained above was punched out so that the outer diameter was 15.0 mm, the length was 15.0 mm, the inner diameter was 14.3 mm, and the length was 14.3 mm. Test piece 1 was prepared. Next, as shown in FIG.
  • a magnesium adherend plate 3 having a square hole 2 in the center is prepared, and the test piece 1 from which the release paper has been peeled off is used as the upper surface of the magnesium adherend plate 3. Then, it was pasted over the entire outer periphery of the hole 2.
  • a glass adherend 4 having a size covering the hole 2 was stacked on the test piece 1 and attached, and the hole 2 was covered to assemble an impact resistance test apparatus. Thereafter, the impact resistance test apparatus is turned upside down so that the magnesium adherend plate 3 is placed on the upper surface, and a pressure of 5 kgf is applied from the magnesium adherend plate 3 side for 5 seconds to position the magnesium adherend located above and below. The platen 3 and the test piece were pressure-bonded and left at room temperature for 36 hours.
  • the manufactured impact resistance test apparatus is fixed to a support base 5, and an iron ball having a weight of 50 g passing through a hole 2 formed in a magnesium adherend plate 3. 6 was dropped to pass through hole 2.
  • an iron ball having a weight of 50 g passing through a hole 2 formed in a magnesium adherend plate 3. 6 was dropped to pass through hole 2.
  • the case where the impact resistance was 23 cm or more was determined as “Pass: ⁇ ”, and the case where it was less than 23 cm was determined as “Fail: X”.
  • a primer was applied to the surface of the cut foam sheet 7 to which the jig 9 was not adhered, and an adhesive 10 having a diameter of 5 mm was dropped onto the center of the applied portion.
  • an adhesive 10 having a diameter of 5 mm was dropped onto the center of the applied portion.
  • a 10 mm square aluminum jig 11 was placed on the adhesive dripping portion, and the foamed sheet 7 and the jig 11 were pressure bonded.
  • cuts 12 were made in the foamed sheet along the size of the jig 11.
  • the adhesive was cured by allowing it to stand at room temperature for 30 minutes to obtain a sample for measuring interlayer strength.
  • Example 1 100 parts by mass of a linear low-density polyethylene resin (trade name “Affinity PL1850”, density: 0.902 g / cm 3 , manufactured by Dow Chemical Co., Ltd.) obtained by a polymerization catalyst of a metallocene compound, and a pyrolytic foaming agent Foamability composed of 2.1 parts by mass of azodicarbonamide (trade name “SO-G3” manufactured by Otsuka Chemical Co., Ltd.), 0.5 parts by mass of an antioxidant and 1.0 part by mass of a cell core modifier.
  • a linear low-density polyethylene resin trade name “Affinity PL1850”, density: 0.902 g / cm 3 , manufactured by Dow Chemical Co., Ltd.
  • Foamability composed of 2.1 parts by mass of azodicarbonamide (trade name “SO-G3” manufactured by Otsuka Chemical Co., Ltd.), 0.5 parts by mass of an antioxidant and 1.0 part by mass of a cell core modifier.
  • the polyolefin resin composition was supplied to an extruder, melted and kneaded at 130 ° C., and extruded into a long polyolefin resin sheet having a thickness of 290 ⁇ m.
  • both sides of the long polyolefin resin sheet are irradiated with 7.4 Mrad of an electron beam with an acceleration voltage of 500 kV to crosslink the foamable polyolefin resin sheet (crosslinking degree: 41.4%), and then the foamable polyolefin resin.
  • the sheet was continuously fed into a foaming furnace maintained at 250 ° C. with hot air and an infrared heater and heated to obtain a foamed sheet having a thickness of 300 ⁇ m.
  • the obtained foamed sheet was continuously fed out from the foaming furnace, and then the foamed sheet was maintained in the TD direction in the state where the temperature of both surfaces thereof was 200 to 250 ° C.
  • Stretching the foamed sheet in the MD direction by winding the foamed sheet at a winding speed faster than the feeding speed (feeding speed) of the foamable polyolefin resin sheet to the foaming furnace while stretching at a stretch ratio of 2 times,
  • the foamed foam sheet was stretched and deformed in the TD direction and MD direction to obtain a crosslinked polyolefin resin foam sheet.
  • the winding speed of the foamed sheet was adjusted in consideration of the expansion in the MD direction due to foaming of the foamable polyolefin resin sheet itself.
  • the obtained crosslinked polyolefin resin foamed sheet was evaluated according to the above evaluation method, and the results are shown in Table 1.
  • Example 2 The same procedure as in Example 1 was performed except that the electron beam irradiation amount was 10.1 Mrad and the degree of crosslinking was 69.1%.
  • the evaluation results of the obtained crosslinked polyolefin resin foam sheet are shown in Table 1.
  • Example 1 Example 1 except that the blending amount of azodicarbonamide in the foamable polyolefin resin composition is 1.6 parts by mass, the electron beam irradiation amount is 4.7 Mrad, and the crosslinking degree is 16.2%. It carried out similarly.
  • the evaluation results of the obtained crosslinked polyolefin resin foam sheet are shown in Table 1.
  • the strain hardening degree ( ⁇ max) obtained from the uniaxial elongation viscosity at a strain rate of 0.2 to 1.0 [1 / s] is 0.1 or more and less than 0.5, and the shear viscosity
  • the slope m of the linear region of ⁇ + and the extension time t [s] satisfies the relationship of 0.7 ⁇ m ⁇ 1.0
  • the strain hardening degree ( ⁇ max) and m are outside the above ranges.
  • the impact resistance and interlayer strength were excellent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

La présente invention concerne une feuille de mousse de résine de polyoléfine réticulée qui comporte des cellules fermées formées dans celle-ci. À la température de formation de mousse et lorsque la vitesse de déformation est de 0,2 à 1,0 [1/s], l'écrouissage (λmax), calculé à partir de la viscosité d'allongement uniaxial, est supérieur ou égal à 0,1 et inférieur à 0,5 ; à la température de formation de mousse, la pente m dans une région linéaire de viscosité de cisaillement η+ et le temps d'allongement t[s] satisfait à 0,7 ≦ m ≦ 1,0, et le diamètre moyen des cellules dans la direction machine et la direction transversale est inférieur ou égal à 120 µm.
PCT/JP2017/013767 2016-03-31 2017-03-31 Feuille de mousse de résine de polyoléfine réticulée et son procédé de production WO2017171063A1 (fr)

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JP2017520993A JP6496407B2 (ja) 2016-03-31 2017-03-31 架橋ポリオレフィン樹脂発泡シート及びその製造方法
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JP6918701B2 (ja) * 2016-09-30 2021-08-11 積水化学工業株式会社 ポリオレフィン系発泡シート、その製造方法及び粘着テープ

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CN108431106B (zh) 2019-11-12
KR102062297B1 (ko) 2020-01-03

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